Electro-chemical sensors for trace gases

ABSTRACT

The disclosure relates to electro-chemical sensors for sensing gaseous nitrogen dioxide in the presence of carbon monoxide, oxygen, nitrogen, sulfur dioxide, nitric oxide and in chemically compatible mixtures of these gases as well as capable of sensing gaseous materials which are more strongly oxidizing than NO2, the sensor being formed from an Fe-1173 glass. The disclosure also relates to an electro-chemical sensor formed from 15% manganese As2S3 glass which is capable of sensing gaseous materials which are more oxidizing than NO2 in the presence of NO2, CO, O2, N2, SO2, NO and in chemically compatible mixtures of these gases. The disclosure also includes apparatus for determining when NO2 is being sensed rather than more strongly oxidizing gaseous materials by the simultaneous use of the Fe-1173 glass electrochemical sensor and the sensor formed from 15% Mn-As2S3 glass.

United States Patent J asinski et al.

1 1 Sept. 30, 1975 ELECTRO-CHEMICAL SENSORS FOR Primary ExaminerT. Tung TRACE GASES Attorney, Agent, or FirmHarold Levine; James T. [75] Inventors: Raymond J. Jasinski; Isaac Comfort; wlmam Hmer Trachtenberg, both of Dallas, Tex.

[73] Assignee: Texas Instruments Incorporated, ABSTRACT Dallas, Tex.

The disclosure relates to electro-chemlcal sensors for [22] Filed: June 18, 1973 sensing gaseous nitrogen dioxide in the presence of carbon monoxide, oxygen, nitrogen, sulfur dioxide, ni- [21] Appl' 370898 tric oxide and in chemically compatible mixtures of these gases as well as capable of sensing gaseous mate- [52] U.S. Cl. 204/195 G; 204/1 T; 204/195 M; rials which are more strongly oxidizing than N0 the 204/195 S sensor being formed from an Fe-l 173 glass. The dis- [51] Int. Cl. G01N 27/46 closure also relates to an electro-chemical sensor [58] Field Of S r h 4/1 195 M, 195 L, formed from 15% manganese AS253 glass which is ca- 204/195 R, 195 S, l T pable of sensing gaseous materials which are more oxidizing than NO; in the presence of N0 CO, 0 N [56] References Cited S0 NO and in chemically1compatible mixtures of UNiTED STATES P S these gases. The disclosure also includes apparatus for 3413199 11/1968 Morrow 204/1 T determining is being i rather 3,539,455 11/1970 Clark 204 195 P more Strongly X1d1lmg gaseous materlals by the 3632487 11/1971 Chand et aL u 204/195 p multaneous use of the Fe-] 173 glass electro-chemical 3,622,488 ll/l97l Chand et a1. 204/195 P sensor and the sensor formed from l5% Mn-As S 3,709,8l3 l/l973 Johnson et,al..1.. 204/195 G glass. 1776.832 l2/l973 Oswin ct al. 204/195 R 1 Claim, 5 Drawing Figures SAMPLE INLET VENT 3, season I 5 1 2.9 E 23 E POWER 25 t SUPPLY //,ELECTROLYTE 9 k REFERENCE COUNTER, 7

US. Patent NORMALIZED CELL POTENTIAL (mV) SAMPLE I //,ELECTROLYTE NLET 3,8ENSOR 1 n I Sept. 30,1975 Sheet 1 of 3 3,909,384

vsm

T PUMP /3 /9 5 23 I 29 v t E POWER suPPLY' .9 F REFERENCE COUNTER, /7 g Ill Illlll IIIIIIIH llllllll |||||l |n||||||| IIIHII Fig. 2

CONCENTRATION NO IN AIR (PPM) US. Patent Sept. 30,1975 Sheet 2 of3 3,909,384

Potential +150 mV vs Ag/AgCl 5 ci'n Electrode CONCENTRATION NO IN AIR (PPM) Fig. 3

US. Patent Sept. 30,1975

Sheet 3 of 3 (RELATIVE TO POTENTIAL UNDER NITROGEN) GAS GLASS Fe-1173 MnO-As S 1173 Air 0 mv 0 mv 10 mv N0, (350 ppm) 365 mv 3 mv 263 mv $02 (100%) 4 mv 0 mv -221 mv C0 (1%) 2 mv 0 mv 90 mv N0 (100 ppm) 2 mv H 9 (0.01%) 54 mv 80 mv CH1 2 mv Key Points Fig. 4

"In Solution Fe-Il73 Cell I5%MnAs S Cell Fig 5 ELECTRO-CI-IEMICAL SENSORS FOR TRACE "GASES This invention relates to an electro-chemical gas sensor cell system capable of continuouslymonitoring gaseous pollutants in ambient urban air, stack gases from' power plants, automobileexhausts-and the like, to determine the presence of N as well as more strongly oxidizing gases, such as ozone, in the presence of CO, 0 N S0 NO and chemically compatible'mixtures of these gases as well as a system for determining when- N0 is the specific one of the gases being sensed.

There has been a general need for low cost equipment to continuously monitor gaspollutants' in ambient urban air, in stack gases for power plants, in automobile exhausts and other pollution causing sources. In

the past, this type of analysis has required going through the costly and slow procedure required by the standard textbooks wherein such gases are passed through a series of liquids to remove certain ones of the gases, one at a time, and determine qualitatively and quantitatively the gases-present.

The prior art has also found diffic'ulty in monitoring low concentrations of N0 and high oxidizing gases at concentrations of 0.01 to 0.1 parts per million by volume. Prior art electrochemical sensors have also had an inherent lack of specificity, insufficient sensitivity to monitor urban air and have been of relatively high cost: Priorart electrochemical sensors have gainedpartial selectivity through the preliminary chemical treatment of the sample gas (selective diffusion through membranes).

In accordance with the present invention, there is provided an electro-chemical gas sensor cell system which is capable of determining when a gas which is as oxidizing as N0 or more'strongly oxidizing, is present .in a gaseous atmosphere containing CO, 0 N S0 NO and chemically compatible mixtures of these gases, which is of relatively lowcost, relatively high sensitivity and capable of specifically identifying N0 both qualitatively and quantitatively. There is also provided a relatively inexpensive electrochemical gas sensor which achieves its great selectivity through the inherent properties of the sensor material itself. In accordance with one embodiment of the invention, there is provided an electrochemical sensor which is composed of Fe-1l73 glass, as will be explained in more detail hereinbelow,

which is capable of providing a voltage between the sensor and a reference electrode which issepara ted from the sensor by an electrolyte to providean output voltage which is linearly related to the logarithm of the concentration of N0 passing over the sensor.

' In accordance with a second embodiment 'of the invention, the sensor is formed from Mn-As- S glass which is 15 mole percent MnO fused into a substrate of arsenic trisulfide. This sensor will detect gases which are more strongly oxidizing than N0 but will not detect NO in the same environment as discussed above.

In accordance with a third embodiment of the invention, a predetermined voltage is presented across the sensor and the reference electrode and a current is passed between the sensor and a counter electrode which is separated from the sensor electrode by the same electrolyte. In this case, the current passing through the sensor to the counter electrode has a direct linear relation to the amount of N0, gas or'more strongly oxidizing gas such as ozone or the like passing across the sensor. In accordance with the third embodiment of the invention, the-sensor is either that of the first or second embodiment.

In accordance with the fourth embodiment of the invention, an electro-chemical gas sensor cell in accordance with the first embodiment of the invention can be used in conjunction with an electro-chemical gas sensor cell in accordance with the second embodiment of the invention, whereby, if each of the sensor cells detects an oxidizing gas it can be determined that this gas is more strongly oxidizing than N0 If only the sensor 7 cell in accordance with-the first embodiment has detected an oxidizing gas whereas the second sensor cell does not, it is immediately determined that N0 is present in the example under test and no gas more strongly oxidizing than N0 is present.

It is therefore an object of this invention to provide a low cost electro-chemical gas sensor cell capable of detecting N0 and more strongly oxidizing gases in the presence of CO 0 N S0 NO and in chemically compatiblemixtures of these gases. i

'It is a further object'of this invention to provide an electro-chemical "gas sensor cell capable of detecting gases more strongly oxidizing than N0 in the presence of CO, 0 N S0 NO, and in chemically compatible mixtures of these gases. It is a yet further object of this invention to provide an electro-chemical gas sensor cell system capable of determin'ingspe'cifically whether NO specifically is present in a sample containing CO, 0 N SO NO and chemically compatible mixtures of gases.

It is a still further object of this invention to provide an electro-chemical gas sensor formed from a chalcogenide glass having at most a small amount of crystalline structure and a resistivity of less than about ten thousand ohm-centimeters.

The above objects and still further objects of the invention will immediately become apparent to those skilled in the art after consideration of the following preferred embodiments thereof, which are provided by way of example and not by way of limitation whereini FIG. 1 is a schematic diagram of an electro-chemical gas sensor cell' in accordance with the first and second embodiments of the present invention;

FIG.'2 is a graph of the voltage output across the sensor and reference electrode of the gas sensor of FIG. 1 in milli'volts 'as' compared with the logarithm of the concentrat'ion of N0 in air in parts per million;

FIG. 3 is a graph of the output current across the sensor and counter electrode of FIG. 1 in microamps as compared with the concentration of N0 in air parts per million passing over the sensor;

FIG. 4 is a chart showing the voltage sensed at the meter'across the sensor and reference electrode of FIG. 1 for various gases passed over the sensor and for various sensors; and

FIG. 5 is a circuit diagram depicting the third embodiment of the present invention.

Referring now to FIG. I, there is shown an electrochemical gas sensor cell in accordance with the first and second embodiments of the present invention. The sensor cell includes a sample inlet 1 for receiving a gas sample to be tested, the sample passing through the cell and over the sensor 3, the gas being drawn to the outlet vent 5 by means of a pump 7 which draws the sample through the cell. The sensor 3 is separated from a reference electrode 9 by an electrolyte 11, an electrically conductive cell housing portion 13 being electrically connected to the sensor 3 and a cell housing portion 15 being electrically connected to the reference electrode 9. The cell also includes a counter electrode 17 which is spaced from the sensor 3 and has an electrolyte 11 between the sensor 3 and the counter electrode 17. An electrically conducting housing portion 19 is connected to the sensor 3 and an electrically conducting housing portion 21 is connected to the counter electrode 17. Electrode 17 is only required when an output in accordance with FIG. 3 is desired. It can be seen that the gas flow will pass through the housing portion 13 which includes the sample inlet 1, over the sensor 3 and out to the outlet vent through the housing portion 19. The housing portions 13, 15, 19 and 21 are secured within an electrically insulating housing member 23 in which the sensor 3, reference electrode 9, counter electrode 17 and electrolyte 11 are also positioned.

The sensor 3 is formed from a chalcogenide glass, one embodiment thereof being an 1 173 glass which has been doped with iron, cobalt, nickel or the selenides of iron, cobalt and nickel as impurities. The 1173 glass is fully set forth in the Journal of the Electro-Chemical Society, Volume 118, No. 4, April 1971, at pages 571-576. This article indicates that such glass in its undoped form comprises 60 mole percent selenium, 28 mole percent germanium and 12 mole percent antimony. The glass in accordance with this embodiment may have small amounts of crystalline structure and will include as much of the dopant as can possibly be added without the dopant appearing in the glass as the free metal. This will provide a resistivity in the range of ohm-centimeters to 50 ohm centimeters or less and preferably 10 ohm-centimeter or less. It has been found that for an iron impurity in the glass, the weight range of the iron is in the range of 1 to 4%. No upper limit has yet been found for the other impurities listed above.

The iron glass is prepared by fusing the appropriate amount of iron wire at 900 to 1000 C. with the glass Se Ge Sb previously synthesized directly from the pure elements and ground up. This provides the non porous glass sensor required in accordance with the present invention. As will be explained in more detail hereinbelow, it has been found that the above described sensor will provide a response to N0 and gases more strongly oxidizing than N0 in the presence of CO, 0 N S0 NO and in chemically compatible mixtures of these gases.

In accordance with the second embodiment of the invention, the sensor 3 is formed from Mn-As s glass. Sensors formed from this glass have been found to be responsive in the manner to be described hereinbelow to gases which are more strongly oxidizing than N0 such as above, but not to N0 The electrolyte 11 is impregnated or soaked into filter paper between the sensor 3 and the electrodes 9 and 17. The electrolyte material is not critical but it can be from concentrated nitric or sulfuric acids to potassium chloride which has a pH of 7, so it can be seen that almost any electrolyte can be utilized.

The counter electrode 17 and reference electrode 9 can be formed of standard materials, such as silver chloride on a silver screen, tantalum, or the like as is well known in the art. Examples of such electrodes are set forth in Reference Electrodes, D. Ives and G. .lanz, Academic Press, NY. 1961, with the proviso that the counter electrode material, on discharge, must not inject electroactive materials into the electrolyte.

It can be seen from the above that the sensor in accordance with the first embodiment will sense any gas which is as oxidizing as N0 or more strongly oxidizing but will not be selective, whereas the sensor in accordance with the second embodiment will only sense any gas which is more strongly oxidizing than N0 but again will not be selective. The sensing of these gases by the sensor 3 is accomplished in the following manners. Referring again to FIG. 1, there is shown a voltmeter 25 connected across the housing portions 13 and 15. This voltmeter will measure an increase in the voltage at the sensor 3 relative to the reference electrode 9 to determine whether one of the gases to which the sensor 3 is responsive is present in the sample being passed into the sample inlet 1 and out through the vent.

FIG. 2 is a graph of the output voltage of a normalized electro-chemical gas sensor cell as set forth in FIG. 1 in millivolts for various concentrations of N0 in air in parts per million. It can be seen that in the logarithmic graph set forth for the concentration of N0 in parts per million, the curve in linear. It has been found by experimentation that this curve actually extends downwardly to concentrations as low as one part per million and is still linear in that range and possibly below that range. It is therefore apparent that not only can the particular gases mentioned above be tested in accordance with this procedure in a qualitative manner but also in a quantitative manner by means of the calibration curve of FIG. 2.

In accordance with the second procedure for measuring the concentration of the gases under test, a voltage is placed across the sensor 3 and the reference electrode 9 and current is passed between the sensor 3 and the counter electrode 17 by means of a power supply 27 as shown in FIG. 1. The current passing between the sensor 3 and the counter electrode 17 is measured by the meter 29. A graph of the results of such measurement is shown in FIG. 3 where it is shown that a linear relationship exists between the current in microamps measured by the ammeter 29 and the concentration of N0 in air in parts per million. The graph in FIG. 3 was provided utilizing a potential across the sensor 3 and the reference electrode 9 of millivolts with an AglAgCl 5 cm electrode. Again, it is apparent that the gases under test can be measured both qualitatively as well as quantitatively in view of the calibration curve set forth in FIG. 3.

Referring now to FIG. 4, there is shown a graph of potential changes across the sensor vs. gas phase composition. Three types of gas sensors of the type described above are utilized, one being the Fe-1173 of the first embodiment, the second being the Mn-As S of the second embodiment and the third being undoped I173 glass which gave no meaningful results whereas when doped with iron there was a significant change in voltage for N0 and for a 0.01% hydrogen peroxide solution. In the case of the manganese oxide arsenic trisulfide glass, the only significant change in voltage appears for the hydrogen peroxide in solution, this material being more strongly oxidizing than N0 The effectiveness of the sensors in accordance with the present invention is therefore demonstrated by this chart.

In view of the ability of the iron doped glass to sense N0 as well as more strongly oxidizing gases whereas the manganese oxide arsenic trisulfide glass is merely capable of sensing gases which are more strongly oxidizing than N the use of two sensors, one using an iron 1173 glass and the other using a manganese oxide arsenic trisulfide glass can-be utilized together to indicate whether the gas being sensed is specifically N0 or some other gas. In FIG. 5, the box 31 is an electro-chemical gas sensing cell of FIG. 1 using an Fe-l 173 sensor whereas box 33 is an electrochemical gas sensor cell as set forth in FIG. 1 using a manganese oxide-arsenic trisulfide glass sensor. An output provided from each of the sensors which can be the output voltage sensed by the voltmeter of FIG. 1 is passed to an OR gate 35 as well as an AND gate 37 having an inhibit electrode 39. It can be seen that OR gate 35 will provide a positive output signal if either cell 31 or cell 33 senses a gas to which it is responsive. Therefore a proper output from OR gate 35 will indicate that N0 or a more strongly oxidizing gas is present. AND gate 37 will provide an output only if a gas to which cell 31 is responsive is present and if a gas to which cell 33 is responsive is not present. Therefore, an output from AND gate 37 is only present when NO 2 specifically has been sensed since if a more strongly oxidizing gas were present, there would be an output signal from both of the cells 31 and 33. It is therefore apparent that the embodiment of FIG. provides a method of specifically determining the presence of N0 relative to the more strongly oxidizing gases which would also operate any one of the cells described herein.

In the fifth embodiment the signals of cell 31 and cell 33 aer compared, taking into account the appropriate voltage-concentration calibration curves such as shown in FIG. 2. This difference signal indicates the quantity of NO present.

Electrodes 3 of the first embodiment were formed by grinding the iron doped 1173 glass, mixing it with polytetrafluoroethylene (Teflon) emulsion and placing the mixture on a tantalum screen. This was placed in an oven with air therein at 290C. for 3 to 5 minutes to remove any wetting agent and allow the polytetrafluoroethylene to flow and bond to the screen. This sensor electrode 3 was used in a cell having an electrolyte 11 of IN KCl, pH 2 soaked into fiber glass filter paper with the reference electrode 9 and the counter electrode 17 being made of silver chloride on a silver screen. The silver-silver chloride screen could be replaced by a tantalum screen. The same electrolyte, reference electrode 7 and counter electrode were also used with the sensor of the second embodiment.

Though the invention has been described with respect to specific preferred embodiments thereof, many variations and modifications will immediately become apparent to those skilled in the art. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications.

What is claimed is:

1. An electro-chemical sensor system comprising:

a first electro-chemical gas sensing cell having a doped chalcogenide glass consisting of about mole percent selenium, 28 mole percent germanium, 12 mole percent antimony and containing as a dopant about 1% to about 4% by weight of iron, an electrical conductor electrically connected to said glass on one side, an electrolyte contacting the other side of said glass, and at least one electrode contacting said electrolyte,

a second electro-chemical gas sensing cell having a doped chalcogenide glass consisting of 15% Mn- As S an electrical conductor electrically connected to said glass on one side, an electrolyte contacting the other side of said glass, and at least one electrode contacting said electrolyte,

means for introducing a gas sample into said first and second cells so as to impinge upon the respective glasses thereof,

said first cell being responsive to the presence of gaseous N0 and more strongly oxidizing gases to produce an electrical signal between the firstmentioned electrical conductor and one of the first-mentioned at least one electrode and said second cell having responsive to the presence of gases more strongly oxidizing than N0 to produce an electrical signal between the second-mentioned electrical conductor and one of the secondmentioned at least one electrode, and

means for measuring the electrical signals developed by said first and second cells in response to the introduction of the gas sample thereinto so as to indicate whether N0 and more strongly oxidizing gases are present in the gas sample. 

1. AN ELECTRO-CHEMICAL SENSOR SYSTEM COMPRISING: A FIRST ELECTRO-CHEMICAL GAS SENSING CELL HAVING A DOPED CHALCOGENIDE GLASS CONSISTING OF ABOUT 60 MOLE PERCENT SELENIUM, 28 MOLE PERCENT GERMANIUM, 12 MOLE PERCENT ANTIMONY AND CONTAINING AS A DOPANT ABOUT 1% TO ABOUT 4% BY WEIGHT OF IRON, AN ELECTRICAL CONDUCTOR ELECTRICALLY CONNECTED TO SAID GLASS ON ONE SIDE, AN ELECTROLYTE CONTACTING THE OTHER SIDE OF SAID GLASS, AN AT LEAST ONE ELECTRODE CONTACTING SAID ELECTROLYTE, A SECOND ELECTRO-CHEMICAL GAS SENSING CELL HAVING A DOPED CHALCOGENIDE GLASS CONSISTING OF 15% MN-AS2S3, AN ELECTRICAL CONDUCTOR ELECTRICALLY CONNECTED TO SAID GLASS ON ONE SIDE, AN ELECTROLYTE CONTACTING THE OTHER SIDE OF SAID GLASS, AND AT LEAST ONE ELECTRDE CONTACTING SAID ELECTROLYTE, MEANS FOR INTRODUCING A GAS SAMPLE INTO SAID FIRST AND SECOND CELLS SO AS TO IMPINGE UPON THE RESPECTIVE GLASSES THEREOF, SAID FIRST CELL BEING RESPONSIVE TO THE PRESENCE OF GASEOUS NO2 AND MORE STRONGLY OXIDIZING GASES TO PRODUCE AN ELECTRICAL SIGNAL BETWEEN THE FIRST-MENTIONED ELECTRICAL CONDUCTOR AND ONE OF THE FIRST-MENTIONED AT LEAST ONE ELECTRODE AND SAID SECOND CELL HAVING RESPONSIVE TO THE PRESENCE OF GASES MORE STRONGLY OXIDIZING THAN NO2 TO PRODUCE AN ELECTRICAL SIGNAL BETWEEN THE SECOND-MENTIONED ELECTRICAL CONDUCTOR AND ONE OF THE SECOND-MENTIONED AT LEAST ONE ELECTRODE, AND MEANS FOR MEASURING THE ELECTRICAL SIGNALS DEVELOPED BY SAID FIRST AND SECOND CELLS IN RESPONSE TO THE INTRODUCTION OF THE GAS SAMPLE THEREINTO SO AS TO INDICATE WHETHER NO2 AND MORE STRONGLY OXIDIZING GASES ARE PRESENT IN THE GAS SAMPLE. 